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The castle was constructed in about 1316/1317. Rheinstein Castle was important for its strategic location. By 1344, the castle was in decline. By the time of the Palatine War of Succession, the castle was very dilapidated. During the romantic period in the 19th century, Prince Frederick of Prussia (1794–1863) bought the castle and it was rebuilt.

1409 – John of Nassau enfeoffed the Geheimrat, Johann von Selheim, with Königstein. Sometimes the archbishops of Mainz stayed here in their secular role as electors of the Holy Roman Empire.

1459 – Diether von Isenburg, Elector and Archbishop of Mainz, enfeoffed the castle and the village of Assmannshausen (which is near the castle on the opposite bank of Rhine) to the cathedral student (Domscholasten) Volpert.

1572 – The castle, together with its associated estate, was transferred to Mainz cathedral's custodian (Domkustos) and chamberlain, Anton Wiltberg. He could not maintain the castle economically, however. It gradually decayed, but remained Wiltberg's residence until his death.

1779 – the ruins were given a new owner: Geheimrat J.von Eys. He alienated the buildings for four Laubtalers to the Regierungsrat Johann Jacob, Lord of Goll.

1825–1829 – saw its rebuilding under the leadership of the famous castle builder, Claudius Lassaulx, who was succeeded in 1827 by his pupil, Wilhelm Kuhn, who completed the building. Prince Frederick named the castle "Rheinstein" because of its impressive cliffs directly above the river.

1842 – Rheinstein Castle became the favorite residence of Prince Frederick. Many crowned heads of state of that time were guests at the castle, such as Queen Victoria, Empress Alexandra Feodorovna of Russia and many others. Prince Frederick had the Wiesbaden architect, Ph. Hoffmann, draw up a plan for a chapel and crypt. Just two years later, the neo-Gothic chapel and crypt for the royal family was formally opened.